Au-activated N motifs in non-coherent cupric porphyrin metal organic frameworks for promoting and stabilizing ethylene production

Xie, Xulan; Zhang, Xiang; Xie, Miao; Xiong, Likun; Sun, Hao; Lu, Yongtao; Mu, Qiaoqiao; Rummeli, Mark H.; Xu, Jiabin; Li, Shuo; Zhong, Jun; Deng, Zhao; Ma, Bingyun; Cheng, Tao; Goddard III, William A.; Peng, Yang

doi:10.1038/s41467-021-27768-6

Title: Au-activated N motifs in non-coherent cupric porphyrin metal organic frameworks for promoting and stabilizing ethylene production

Journal Article · 17 January 2022 · Nature Communications

DOI: https://doi.org/10.1038/s41467-021-27768-6 · OSTI ID:1904263

Xie, Xulan ^[1]; Zhang, Xiang ^[2];

^[3]; Xiong, Likun ^[4]; Sun, Hao ^[5]; Lu, Yongtao ^[2]; Mu, Qiaoqiao ^[2]; Rummeli, Mark H. ^[2]; Xu, Jiabin ^[3]; Li, Shuo ^[3]; Zhong, Jun ^[3];

^[2]; Ma, Bingyun ^[3];

^[3];

^[6];

^[5]

Soochow University, Suzhou (China); Key Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of Jiangsu Province, Suzhou (China); OSTI
Soochow University, Suzhou (China); Key Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of Jiangsu Province, Suzhou (China)
Soochow University, Suzhou (China)
Shanghai Institute of Technology, Shanghai (China)
Soochow University, Suzhou (China); Key Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of Jiangsu Province, Suzhou (China); Jiangsu Engineering Laboratory of New Materials for Sewage Treatment and Recycling, Suzhou (China)
California Institute of Technology (CalTech), Pasadena, CA (United States)

Direct implementation of metal-organic frameworks as the catalyst for CO₂ electroreduction has been challenging due to issues such as poor conductivity, stability, and limited > 2e^- products. In this study, Au nanoneedles are impregnated into a cupric porphyrin-based metal-organic framework by exploiting ligand carboxylates as the Au³⁺ -reducing agent, simultaneously cleaving the ligand-node linkage. Surprisingly, despite the lack of a coherent structure, the Au-inserted framework affords a superb ethylene selectivity up to 52.5% in Faradaic efficiency, ranking among the best for metal-organic frameworks reported in the literature. Through operando X-ray, infrared spectroscopies and density functional theory calculations, the enhanced ethylene selectivity is attributed to Au-activated nitrogen motifs in coordination with the Cu centers for C-C coupling at the metalloporphyrin sites. Furthermore, the Au-inserted catalyst demonstrates both improved structural and catalytic stability, ascribed to the altered charge conduction path that bypasses the incoherent framework. This study underlines the modulation of reticular metalloporphyrin structure by metal impregnation for steering the CO₂ reduction reaction pathway.

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Research Organization:: California Institute of Technology (CalTech), Pasadena, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China; Natural Science Foundation of Jiangsu Province; National Key R&D Program of China; Natural Science Foundation of Jiangsu Higher Education Institutions; Six Talent Peaks Project in Jiangsu Province; Soochow University; Collaborative Innovation Center of Suzhou Nano Science & Technology

Grant/Contract Number:: SC0021266

OSTI ID:: 1904263

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 13; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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